JPH02123183A - Adhesive, bonding method using same and formed hose using same and production thereof - Google Patents

Abstract

PURPOSE:To obtain an adhesive excellent in resistance to oil and heat for organic peroxide-curing rubber compositions based on ethylene elastomer by dissolving in a solvent a rubber composition prepared by incorporating a copolymer rubber with an organosulfur compound and organic peroxide curing agent at each specified amount. CONSTITUTION:The objective adhesive can be obtained by dissolving in a solvent such as methyl ethyl ketone a rubber composition prepared by incorporating (A) 100 pts.wt. of a copolymer rubber from (1) 10-45wt.% of a unsaturated nitrile, (2) 0-20wt.% of a conjugated diene, and (3) 90-35wt.% of an ethylenic unsaturated monomer except unsaturated nitrile and/or hydrogenated product from conjugated diene, with (B) 0.1-15 pts.wt. of an organosulfur compound pref. consisting of 6-R-2,4-dimercapto-1,3,5-triazine [R is mercapto, alkoxy, (di) alkylamino, etc.] and (C) 1-15 pts.wt. of an organic peroxide curing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an adhesive suitable for adhering organic peroxide vulcanized rubber compositions of ethylene-based elastomers.

The present invention also relates to an adhesion method using an organic peroxide vulcanized rubber composition of an ethylene-based elastomer as an adherend.

Furthermore, the present invention has an inner tube, a roughly braided reinforcing layer, and an outer tube, the inner tube and the outer tube are made of an organic peroxide vulcanized rubber composition of an ethylene-based elastomer, and the inner tube and The present invention relates to a molded hose having an adhesive rubber composition layer between the outer tube and a method for manufacturing the same.

<Prior Art> In recent years, many rubber products such as tires, belts, molds, rolls, and hoses have been used for long periods of time with heated oil under high temperature and pressure. Product deterioration is always a serious problem. This is because if the rubber product deteriorates significantly, a great deal of time and effort is required for maintenance and replacement, and furthermore, the deterioration of the rubber product may cause a major accident.

It has excellent oil resistance and can withstand such high temperatures (120~150℃).
) Acrylonitrile-butadiene co-rM polymer rubber (NBR
), acrylic rubber (ACM), ethylene-acrylic rubber (AEM), ethylene-acrylic-vinyl acetate copolymer rubber (ER), chlorosulfonated polyethylene rubber (
CSM) Chlorinated polyethylene rubber (CM), and acrylonitrile-butadiene copolymer rubber (N B
Rubbers such as R) in which the conjugated diene portion of an acrylonitrile copolymer rubber is hydrogenated are known.

In addition, among rubber products, organic peroxide vulcanized rubber compositions that use organic peroxides have better heat resistance than sulfur vulcanized rubber compositions that use sulfur during vulcanization. It is known that there are

By the way, suitable adhesives such as phenol resin-based, epoxy resin-based, cyanate-based adhesives and adhesive compositions are used for adhering rubber to each other or to adhering rubber to adherends made of other materials. Phenolic resin adhesives are used to bond organic peroxide vulcanized rubber compositions.

However, when an organic peroxide vulcanized rubber composition is bonded using a phenolic resin adhesive, a sufficient chemical bond is not formed between the adherend and the adhesive. , the adhesive layer has insufficient heat resistance and durability, and the desired adhesive performance cannot be obtained. Furthermore, other than phenolic resin adhesives, no adhesives are known that are effective for organic peroxide vulcanized rubber compositions.

Therefore, an adhesion method using an organic peroxide vulcanized rubber composition of an ethylene elastomer as an adherend, or an adhesive method having an inner tube, a reinforcing layer, and an outer tube, in which the inner tube and the outer tube are made of an organic peroxide vulcanized rubber composition of an ethylene elastomer. A molded hose made of a peroxide vulcanized rubber composition and having an adhesive rubber composition layer between an inner tube and an outer tube, and a method for manufacturing the same, are also not known.

<Problems to be Solved by the Invention> The present invention has been made in view of the above facts, and has oil resistance and heat resistance suitable for adhesion between organic peroxide vulcanized rubber compositions of ethylene-based elastomers. The purpose is to provide adhesives.

Another object of the present invention is to provide an adhesion method for adhering organic peroxide vulcanized rubber compositions of ethylene-based elastomers.

Furthermore, the present invention has an inner tube, a roughly braided reinforcing layer, and an outer tube, the inner tube and the outer tube are made of an organic peroxide vulcanized rubber composition of an ethylene-based elastomer, and the inner tube and The object of the present invention is to provide an oil- and heat-resistant molded hose having an adhesive rubber composition layer between the outer tube and a method for manufacturing the same.

<Means for Solving the Problems> The present invention uses an organic peroxide vulcanized rubber composition of an ethylene-based elastomer as an adherend, interposes it between the adherends, and then vulcanizes and integrates the adherend. An adhesive used for bonding adherends, comprising 10 to 45% by weight of units from unsaturated nitrile and 0 to 20% by weight of units from conjugated diene and unsaturated nitrile in the polymer chain. Unit parts 90 to 35 hydrogenated to unit parts derived from ethylenically unsaturated monomers other than and/or unit parts derived from conjugated dienes
0.1 to 15 parts by weight of an organic sulfur-containing compound and 1 to 15 parts by weight of an organic peroxide vulcanizing agent (as a net amount of organic peroxide) per ioo parts by weight of a copolymer rubber having % by weight. The present invention provides an adhesive characterized in that the rubber composition is dissolved in a solvent.

Further, the present invention uses an organic peroxide vulcanized rubber composition of ethylene-based elastomer as an adherend, interposes an adhesive between the adherends, and then vulcanizes and integrates the adherend. In the adhesion method, the polymer chain contains 10 to 45% by weight of units from unsaturated nitrile, 0 to 20% by weight of units from conjugated diene, and ethylenically unsaturated monomers other than unsaturated nitrile. Unit part 9 hydrogenated to a unit part from and/or a unit part from a conjugated diene
0 to 35% by weight of copolymer rubber, 061 to 15 parts by weight of an organic sulfur-containing compound, and 1 to 15 parts by weight of an organic peroxide vulcanizing agent (as a net amount of organic peroxide). The object of the present invention is to provide an adhesion method characterized by using a rubber composition formed by blending the above rubber composition or an adhesive formed by dissolving the rubber composition in a solvent.

Furthermore, the present invention provides a molded hose having an inner tube, a roughly braided reinforcing layer, and an outer tube, the inner tube and the outer tube being made of an organic peroxide vulcanized rubber composition of an ethylene elastomer. The present invention provides a molded hose characterized by having a layer made of the following rubber composition between the inner tube and the outer tube.

(Rubber composition) 10 to 4 units of unsaturated nitrile in the polymer chain
5% by weight and unit portion from conjugated diene 0-20% by weight
and 90 to 35% by weight of a hydrogenated unit part from an ethylenically unsaturated monomer other than unsaturated nitrile and/or a unit part from a conjugated diene...too parts by weight organic Sulfur-containing compound: 0.1 to 15 parts by weight Organic peroxide vulcanizing agent (as the net amount of organic peroxide)
In addition to 1 to 15 parts by weight, the present invention has an inner tube, a coarsely braided reinforcing layer, and an outer tube, and the inner tube and the outer tube are made of organic peroxide vulcanized rubber made of ethylene-based elastomer. When manufacturing a molded hose made of the composition, a layer made of the following rubber composition is provided above and/or below the reinforcing layer roughly braided on the inner tube, or the rubber composition is dissolved in a solvent. The present invention provides a method for manufacturing a molded hose, in which an adhesive is applied, an outer tube is provided thereon, a mandrel core of a certain shape is inserted into the inner tube, and the hose is then vulcanized and integrated. be.

(Rubber composition) 10 to 4 units of unsaturated nitrile in the polymer chain
5% by weight and the unit portion of conjugated diene from 0 to 20% by weight
A copolymer rubber having 90 to 35% by weight of a hydrogenated unit part from an ethylenically unsaturated monomer other than unsaturated nitrile and/or a unit part from a conjugated diene...100 parts by weight organic Sulfur-containing compound...0.1 to 15 parts by weight Organic peroxide vulcanizing agent (as the net amount of organic peroxide)...
1 to 15 parts by weight In each of the above inventions, the organic sulfur-containing compound has the general formula; , mono- or di-arylamino group,
It is a group selected from the group consisting of N-alkyl-N'-arylamino groups. ) It is preferable that it is a compound shown by these.

The present invention will be explained in detail below.

In a first aspect of the present invention, an organic peroxide vulcanized rubber composition of an ethylene-based elastomer is used as an adherend, and the adherend is interposed between the adherends, and then vulcanized and made into a stock. An object of the present invention is to provide an adhesive used for bonding.

The target adherend of the adhesive of the present invention is an organic peroxide vulcanized rubber composition of an ethylene elastomer, and examples of the ethylene elastomer include chlorinated polyethylene,
Examples include hydrogenated acrylonitrile copolymer rubber such as hydrogenated NBR. In addition, examples of the vulcanizing agent contained in the rubber composition include dicumyl peroxide, 1,3-bis(t
-butyl bicarbonate diisopropyl)benzene, 4.4-
Examples include organic peroxide vulcanizing agents such as di-t-butyl n-butyl peroxyvalerate. Note that the rubber composition may contain commonly used compounding agents such as vulcanization accelerators, fillers, plasticizers, and anti-aging agents.

The adhesive of the present invention contains the following hydrogenated acrylonitrile copolymer rubber such as hydrogenated NBR as the copolymer rubber.

That is, one unit of unsaturated nitrile is added to the polymer chain.
0-45% by weight, 0-20% unit portion from conjugated diene
It is a copolymer rubber having 90 to 35% by weight of hydrogenated unit parts from ethylenically unsaturated monomers other than unsaturated nitriles and/or unit parts from conjugated dienes, and saturated methylene Spear part (-C-C
-), a nitrile group moiety (ACN), and a carbon-carbon double bond moiety (-C=C-).

Here, the nitrile group moiety (ACN) is a position moiety,
It is 10 to 45% by weight.

If it is less than 10% by weight, oil resistance will be poor, and if it exceeds 45% by weight, cold resistance will be poor.

The carbon-carbon double bond moiety (-C=C-) is, for example, -(
-(: It is a unit portion of a conjugated diene represented by L-CH-CH-C1h+, and is 0 to 20% by weight. Outside this range, resistance to deteriorated oil is poor.

The saturated methylene daughter moiety (-C-C-) is ÷co, -
It is a unit part obtained by hydrogenating a unit part from an ethylenically unsaturated monomer other than unsaturated nitrile and/or a unit part from a conjugated diene represented by cH, →, and 90 to 3
It is 5% by weight. In addition, when high resistance to deteriorated oil is required, the hydrogenation rate is preferably 95% or more.

If the content of saturated methylene 1ff (-C-C-) exceeds 90% by weight, the unit portion (ACN) from unsaturated nitrile will be relatively reduced, the oil resistance will be poor, and the product will not be usable. Also,
When the saturated methylene chain (-C-C-) is less than 35% by weight and the unit moiety from unsaturated nitrile (ACN) is large,
Poor cold resistance, less than 35% by weight of saturated methylene chains (-C=C-), unit moiety from unsaturated nitrile (ACN)
If the number of carbon-carbon double bond moieties (-C=C-) increases, the resistance to deteriorated oil will deteriorate.

Specific examples of such copolymer rubbers include hydrogenated acrylonitrile-butadiene copolymer rubber, acrylonitrile-isoprene copolymer rubber, acrylonitrile-butadiene-isoprene copolymer rubber, etc.; acrylonitrile-butadiene-methyl acrylate copolymer rubber ,
Acrylonitrile-butadiene-acrylate copolymer rubber, etc. and their hydrogenated products; acrylonitrile-ethylene-butadiene copolymer rubber, acrylonitrile-butyl acrylate-ethoxyethyl acrylate-vinyl chloroacetate copolymer rubber, acrylonitrile-butyl acrylate-ethoxyethyl acrylate Examples include -vinylnorbornene copolymer rubber and hydrogenated products thereof.

These copolymer rubbers may be used alone or in combination of two or more, and in some cases in combination with other rubbers within the scope of the invention.

Further, the adhesive of the present invention contains an organic sulfur-containing compound. The organic sulfur-containing compound is preferably 6-R-2,4-dimercapto-1,3,5-1-riazine.

Here, 8-R-2,4-dimercapto-1,3,5-
Triazine is a group of compounds represented by general formula (1).

H In the above formula, R is a mercapto group, an alkoxy group, a mono- or di-alkylamino group, a mono- or di-cycloalkylamino group, a mono- or di-arylamino group, N
-Alkyl-N'-arylamino group.

Among the 6-R,-2,4-dimercapto-1,3,5-triazines, 2,4,6-dimercapto-1
．． 3,5-triazine is preferred.

As the organic sulfur-containing compound, commonly used sulfur donors can be used in addition to those mentioned above.

A sulfur donor is a substance that separates and releases sulfur as active sulfur during a vulcanization reaction among compounds containing sulfur and acts as a vulcanizing agent. Specifically, it has the formula (R2N-C5)t S2 [ In the formula, R represents an alkyl group (however, two R's may be connected to form a ring) or a hydrogen atom, and may be one type or two or more types. ] Thiuram disulfide such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, dipentamethylenethiuram disulfide, formula (R, □N-C3)t Sd U, where R is an alkyl group (however, two R 4.4'-dithiomorpholine , dimorpholine disulfide, 2-(4-morpholinodithio)benzothiazole, and other morpholine derivatives.

The organic sulfur-containing compound is the copolymer rubber io.

0.1 to 15 parts by weight, preferably 0.5 to 15 parts by weight
Add 10 parts by weight. This is because if the amount is less than 0.1 part by weight, the adhesive strength will be extremely low, and even if more than 15 parts by weight is added, no improvement in adhesive strength can be expected.

Furthermore, the adhesive of the present invention contains an organic peroxide vulcanizing agent. The organic peroxide used as the vulcanizing agent may be any organic peroxide as long as the crosslinking reaction does not proceed to an extreme extent at the temperature during vulcanization, but preferably one with a half-life of 10 hours and a decomposition temperature of 80°C or higher. Certain dialkyl peroxides are good,
Specifically, dicumyl peroxide, 1,3-bis(
t-butylperoxyisopropyl)benzene, 4,4
-di-t-butylperoxyvalerate n-butyl and the like.

The organic peroxide vulcanizing agent is blended in a net amount of 1 to 15 parts by weight based on 100 parts by weight of the copolymer rubber. If it is less than 1 part by weight, it is difficult to develop physical properties, and if it exceeds 15 parts by weight, the organic peroxide residue will affect heat aging, which is not preferable.

The adhesive of the present invention is obtained by dissolving a rubber composition consisting of the above-mentioned copolymer rubber, an organic sulfur-containing compound, an organic peroxide vulcanizing agent, etc. in a solvent. If necessary, a rubber composition may be prepared by blending and kneading commonly used compounding agents such as fillers, reinforcing agents, plasticizers, and anti-aging agents.

The solvent used in the adhesive of the present invention is preferably one that is compatible with the hydrogenated acrylonitrile copolymer rubber such as hydrogenated NBR and that evaporates appropriately at room temperature, and specifically, methyl ethyl ketone or the like is preferable.

Moreover, the proportion of the rubber composition in the adhesive is 5 to 50 w
/v% is good. If it is less than 5 w/v%, the adhesive rubber composition layer becomes too thin and a sufficient adhesive effect cannot be obtained, and if it exceeds 50 w/v%, the solution viscosity becomes high,
Coating workability deteriorates.

A second aspect of the present invention is to use an organic peroxide vulcanized rubber composition of ethylene-based elastomer as an adherend, interpose an adhesive between the adherends, and then vulcanize and integrate the composition. An object of the present invention is to provide an adhesion method for adhering the adherends.

The adhesive used in the finishing method is the adhesive described in the first aspect of the present invention, or a rubber composition that is an adhesive component in the adhesive.

In the final method, an organic peroxide vulcanized rubber composition of ethylene-based elastomer is used as an adherend, and an adhesive is applied between the adherends,
They are interposed by a method such as lamination, and then vulcanized and integrated by a conventional method such as press vulcanization, steam vulcanization, hot water vulcanization, etc. at a temperature of 130 to 200°C. The adherends are adhered, but at this time, the organic sulfur-containing compound such as 6-R-2,4-dimercapto-1,,3,5-triazine in the adhesive reacts with the organic peroxide of the ethylene elastomer. It is believed that the crosslinking reaction with the sulfur rubber composition made it possible to bond organic peroxide vulcanized rubber compositions of ethylene-based elastomers to each other, which was previously difficult.

A third aspect of the present invention has an inner tube, a roughly braided reinforcing layer, and an outer tube, the inner tube and the outer tube being made of an organic peroxide vulcanized rubber composition of an ethylene-based elastomer, It is an object of the present invention to provide a molded hose having a layer of an adhesive rubber composition between an inner tube and an outer tube.

The organic peroxide vulcanized rubber composition of ethylene elastomer forming the inner tube and outer tube of the molded hose is as described in the first aspect of the present invention.

Further, in the molded hose, a layer of a rubber composition, which is an adhesive component in the adhesive described in the first aspect of the present invention, is added to the loosely bonded reinforcing layer between the inner tube and the outer tube. is provided. The fiber material of the reinforcing layer is a commonly used fiber material such as polyester fiber or polyamide M fiber.

In addition, the molded hose is vulcanized during its manufacturing process, and the vulcanization causes the rubber composition that forms the inner tube and outer tube, which are the adherends, and the 6-R in the adhesive rubber composition. A crosslinking reaction occurs with an organic sulfur-containing compound such as -2,4-dimercapto-1°3,5-triazine, and the inner tube and outer tube are sufficiently bonded. A molded hose with excellent oil resistance and heat resistance is thus obtained.

A fourth aspect of the present invention has an inner tube, a roughly braided reinforcing layer, and an outer tube, the inner tube and the outer tube being made of an organic peroxide vulcanized rubber composition of ethylene-based elastomer, The object of the present invention is to provide a method for manufacturing a molded hose in which an inner tube and an outer tube are bonded with an adhesive or an adhesive rubber composition.

The manufacturing method consists of an inner tube extrusion step, a braiding step, an adhesive coating or lamination step of an adhesive rubber composition, an outer tube extrusion step, a mandrel insertion step, a vulcanization step, a mandrel insertion step, and a finishing step. The details are as follows.

That is, the inner tube rubber composition is extruded using an extruder, and a reinforcing layer is roughly braided thereon using a braiding machine. Next, the adhesive described in the first aspect of the present invention is applied onto the reinforcing layer, or a rubber composition which is an adhesive component in the adhesive is laminated, and an outer tube rubber is further applied on top of the reinforcing layer. Extrude the composition using an extruder.

Here, the adhesive may be applied before braiding, or may be applied both before and after braiding.

However, in order to allow the adhesive to penetrate into the reinforcing layer and to strengthen the adhesion between the inner tube and the outer tube, it is better to apply the adhesive after the JJa braiding, and it is sufficient to apply the adhesive only after the braiding.

Further, the adhesive rubber composition may be laminated on the inner tube outer layer below the reinforcing layer, or may be laminated both above and below the reinforcing layer.

Furthermore, even when an adhesive is used instead of an adhesive rubber composition,
Since the solvent is volatilized during the subsequent vulcanization process, what remains in the reinforcing layer portion of the molded Mohose is a layer of the adhesive rubber composition.

A mandrel core shaped into a predetermined shape is inserted into the inner tube of this unvulcanized hose, and then this unvulcanized hose containing the mandrel is vulcanized as described in the second aspect of the present invention,
Unify.

After vulcanization, the mandrel is removed and finishing is performed to obtain the molded hose of the present invention.

<Example> The present invention will be specifically explained below based on Examples.

A rubber composition (adherent) whose composition is shown in Table 1 and an adhesive rubber composition whose composition is shown in Table 2 were prepared, and each was mixed on a mixing roll at 60°C for 15 minutes. A sheet was rolled out to a thickness of 2.5 mm using a small roll for use as a sample for each test shown below.

(Example 1) As shown in Table 3, the adherend and the adhesive rubber composition were combined and pressed using a laboratory press molding machine at 153°C for 90 minutes at a surface pressure of 30 kgf/cm. Sulfurized and molded into one piece.

After standing at room temperature for 24 hours, the sample was cut to a width of 2.54 cm and subjected to a peel test.

The initial adhesive strength was measured using a tensile tester specified in JIS K6301 at a tensile speed of 50 mm/min.
The peel force was calculated in accordance with the method described in JIS 63017.4.3, and was used as initial adhesive force data.

The adhesive strength when hot is 6 according to JIS similar to the above with a constant temperature bath.
Using a tensile tester specified in 301, the measurement was carried out at 120° C. at a tensile speed of 50 mm/min, and the peel force was calculated in the same manner as above and used as hot adhesive force data.

In addition, the peeling state was observed and evaluated based on the peeling force.

The evaluation criteria are as follows.

(Evaluation criteria for adhesion state when heated) ◎: Adherent rubber material failure; peeling force 3 kgf/2, 54 cm or more O: Adherent rubber material failure: peeling force 2 to 3 kgf/2. 54cm △: Adherent rubber material fracture; Peeling force 1-2 kgf72. 54cm X: The peeling results at the adherend/adhesive rubber composition interface are shown in Table 3.

(Example 2) The adherends and adherends were combined as shown in Table 4, and the adhesive rubber composition shown in Table 2, Formulation B-6 was dissolved in methyl ethyl ketone at 20 w/v%. Adhesive (example of the present invention), or phenolic resin adhesive Chemlock 246 (manufactured by Rohto Far East Inc.; dissolved in methyl ethyl ketone/toluene mixed solvent at 20 w/v%) (comparison) Example) was applied between the adherends, and pressure-vulcanized at 153°C for 90 minutes at a surface pressure of 3°kgf/cm' using a laboratory press molding machine to form an integral piece.

The initial adhesive strength and hot adhesive strength were measured and evaluated in the same manner as in Example 1, and the results are shown in Table 4.

(Example 3) A molded hose was produced according to the following method according to the specifications shown in Table 5, and the following tests were conducted.

Method for manufacturing a molded hose> (1) Inner tube extrusion step An inner tube having dimensions of 12.7 mm in inner diameter and 1.8 mm in wall thickness was extruded by extrusion 1.

(2) Reinforcement layer braiding process The polyester fiber reinforcement material was roughly braided using a braiding machine.

(3) Adhesive application step The same adhesive as in Example 2 was applied to the inner tube after reinforcing layer braiding.

(4) Outer tube extrusion process Furthermore, an outer tube having an outer diameter of 19.8 mm was extruded using an extruder.

(5) Mandrel insertion step An iron mandrel of a predetermined shape was inserted into the inner tube of this unvulcanized hose.

(δ) Vulcanization process The unvulcanized hose inserted into the mandrel is heated by a vulcanizer for 16 minutes.
Vulcanization was carried out at 0°C for 90 minutes.

(7) Mandrel extraction process Remove the iron mandrel from the hose after vulcanization.

Hose performance test> (1) Adhesion test The adhesive force between the inner tube/reinforcement layer and the adhesive force between the outer tube/reinforcement layer was determined according to JIS 63017. Measurement was performed based on a peel test (ring-shaped test piece).

(2) Burst pressure (pressure resistance test) Measured in accordance with JIS K63497.3 (3) Burst test.

(3) (High Temperature) Impact Pressure Test According to SAE JIS9, tests were conducted up to 1 million times with n=3.

Temperature: Both oil temperature and outside temperature are the same temperature (150℃), and the operating pressure is 15kgf/cm2 (equivalent to Type I).
Oil used: 5AE10W equivalent oil No. 41 on surface adherend: Parts by weight) (Unit: parts by weight) Surface adhesive rubber composition (Table 2, 1 CM rubber composition (Unit: parts by weight) (Second) Table 2) H5N rubber composition (4 t'-weight parts) (Description of raw materials used) (Product name) Elasuren 301A Asahi #50 OP AIC AP (Daiso Tsubu monomer) (Manufacturer) Showa Denko Asahi Carbon Nisso Sekiyu Chemical Nippon Kasei Osaka Soda (Chemical composition) Chlorinated polyethylene SRF grade carbon black 2-ethylhexyl phthalate triallyl isocyanurate diallyl phthalate Vulkanox DDA Bayer diphenylamine derivative PE 520 Witamol 218 Hoechst AG Wax dynamite/Nobel trimellitic acid ester elas Ren 3
03 Showa Denko Ebicoat 828 Shell Chemical Chlorinated Polyethylene Epoxy Resin Asahi Thermal Asahi Carbon FTF Grade Carbon Black As is clear from Table 3, organic peroxide vulcanized rubber composition of ethylene elastomer (adherent) and book The adhesive properties (initial adhesive strength, hot adhesive strength) with the rubber composition containing the hydrogenated NBR2 organic sulfur-containing compound and the organic peroxide vulcanizing agent, which are the adhesive components of the adhesive of the invention, are extremely high. Are better.

On the other hand, the adhesion between the adherend and a rubber composition containing no organic sulfur-containing compound (Comparative Example 1.3) and the adhesion between the adherend and a rubber composition containing a polymer other than hydrogenated NBR (Comparative Examples 1.2) are inferior to the above-mentioned examples of the present invention.

Furthermore, as is clear from Table 4, when the adhesive of the present invention is used to bond organic peroxide vulcanized rubber compositions of ethylene elastomers together, organic peroxide vulcanization of ethylene elastomers Adhesive properties (initial adhesive strength, hot adhesive strength) are extremely superior compared to the case where phenolic resin adhesives are used to adhere rubber compositions together.

Furthermore, as is clear from Table 5, the adhesive of the present invention is used in the production of a molded hose having inner and outer tubes made of an organic peroxide vulcanized rubber composition of ethylene-based nylastomer and a reinforcing layer of polyester fibers. Compared to the case of using phenolic resin adhesives, which have been used to bond organic peroxide vulcanized rubbers of ethylene elastomers together, the adhesive properties (initial adhesion strength, adhesive strength)
Since the heat resistance and durability of the adhesive rubber composition layer is extremely excellent, the heat resistance and oil resistance, which are the characteristics of the organic peroxide vulcanized rubber composition of the ethylene elastomer, are fully utilized, making the hose durable. The durability of the high temperature impact pressure test, which indicates the lifespan, has been significantly improved.

<Effects of the Invention> The adhesive of the present invention has an adhesive component consisting of organic peroxide vulcanized hydrogenated NBR and 6-R-2,4-dimercapto-1,3.
This adhesive rubber composition contains a predetermined amount of organic sulfur-containing compounds such as , 5-triazine, etc., and has extremely excellent heat resistance and oil resistance.

Furthermore, the present invention proposes a method for adhering an organic peroxide vulcanized rubber composition to an ethylene elastomer using the above adhesive or the above adhesive rubber composition which is an adhesive component of this adhesive. Therefore, it is now possible to bond organic peroxide vulcanized rubber compositions of ethylene-based elastomers together, which has been difficult in the past, and belts, rolls, etc. that are excellent in heat resistance and oil resistance are provided.

Furthermore, the present invention provides a molded hose having an inner tube, a roughly braided reinforcing layer, and an outer tube, the inner tube and the outer tube being made of an organic peroxide vulcanized rubber composition of an ethylene-based elastomer, Since a molded hose having an S-contacting layer made of the adhesive rubber composition described above between the inner tube and the outer tube and a method for manufacturing the same have been proposed, a molded hose with excellent heat resistance and oil resistance is provided.

Claims (8)

[Claims] (1) Adhesive used to bond the adherends by using an organic peroxide vulcanized rubber composition of ethylene-based elastomer as an adherend, interposing it between the adherends, and then vulcanizing and integrating the adherends. an agent containing 10 to 4 units of unsaturated nitrile in the polymer chain.
5% by weight and unit portion from conjugated diene 0-20% by weight
and 90 to 35% by weight of a unit portion obtained by hydrogenating a unit portion from an ethylenically unsaturated monomer other than unsaturated nitrile and/or from a conjugated diene, an organic Sulfur-containing compound 0.1-1
5 parts by weight of an organic peroxide vulcanizing agent and 1 to 15 parts by weight of an organic peroxide vulcanizing agent (as a net amount of organic peroxide), which is dissolved in a solvent. (2) The organic sulfur-containing compound has the general formula; or di-cycloalkylamino group, mono- or di-arylamino group,
It is a group selected from the group consisting of N-alkyl-N'-arylamino groups. ) The adhesive according to claim 1, which is a compound represented by: (3) using an organic peroxide vulcanized rubber composition of ethylene-based elastomer as an adherend, interposing an adhesive between the adherends,
In an adhesion method in which the adherend is then bonded by vulcanization, 10 to 4 units of unsaturated nitrile are added to the polymer chain.
5% by weight and unit portion from conjugated diene 0-20% by weight
and 90 to 35% by weight of a unit portion obtained by hydrogenating a unit portion from an ethylenically unsaturated monomer other than unsaturated nitrile and/or from a conjugated diene, an organic Sulfur-containing compound 0.1-1
5 parts by weight and 1 to 15 parts by weight of an organic peroxide vulcanizing agent (as the net amount of organic peroxide), or an adhesive obtained by dissolving the rubber composition in a solvent. An adhesion method characterized in that it is used. (4) The organic sulfur-containing compound has the general formula; or di-cycloalkylamino group, mono- or di-arylamino group,
It is a group selected from the group consisting of N-alkyl-N'-arylamino groups. ) The bonding method according to claim 3, wherein the bonding method is a compound represented by: (5) A molded hose having an inner tube, a roughly braided reinforcing layer, and an outer tube, the inner tube and the outer tube being made of an organic peroxide vulcanized rubber composition of an ethylene elastomer; A molded hose characterized by having a layer made of the following rubber composition between the tube and the outer tube. (Rubber composition) 10 to 4 units of unsaturated nitrile in the polymer chain
5% by weight and unit portion from conjugated diene 0-20% by weight
Copolymer rubber having 90 to 35% by weight of hydrogenated units from ethylenically unsaturated monomers other than unsaturated nitrile and/or conjugated dienes...100 parts by weight organic Sulfur-containing compound...0.1-15 parts by weight Organic peroxide vulcanizing agent (as net amount of organic peroxide)...1-1
5 parts by weight (6) The organic sulfur-containing compound has the general formula; or di-cycloalkylamino group, mono- or di-arylamino group,
It is a group selected from the group consisting of N-alkyl-N'-arylamino groups. ) The molded hose according to claim 5, which is a compound represented by: (7) When manufacturing a molded hose that has an inner tube, a roughly braided reinforcing layer, and an outer tube, the inner tube and the outer tube are made of an organic peroxide vulcanized rubber composition of ethylene-based elastomer, A layer made of the following rubber composition is provided on and/or below the reinforcing layer roughly braided on the inner tube, or an adhesive made by dissolving the rubber composition in a solvent is applied, and then A method for manufacturing a molded hose, in which an outer tube is provided on top, a mandrel core of a certain shape is then inserted into the inner tube, and then vulcanized and integrated. (Rubber composition) 10 to 4 units of unsaturated nitrile in the polymer chain
5% by weight and unit portion from conjugated diene 0-20% by weight
Copolymer rubber having 90 to 35% by weight of hydrogenated units from ethylenically unsaturated monomers other than unsaturated nitrile and/or conjugated dienes...100 parts by weight organic Sulfur-containing compound...0.1-15 parts by weight Organic peroxide vulcanizing agent (as net amount of organic peroxide)...1-1
5 parts by weight (8) The organic sulfur-containing compound has the general formula: 6-R-2,4-dimercapto-1,3,5-triazine (where R is a mercapto group, an alkoxy group, a mono- or di-alkylamino group, or di-cycloalkylamino group, mono- or di-arylamino group,
It is a group selected from the group consisting of N-alkyl-N'-arylamino groups. ) The method for producing a molded hose according to claim 7, wherein the compound is a compound represented by: